Azo pigments with an anthraquinonyl component and a {62 -hydroxynaphthoic acid component substituted by a trimellitic acid imide via an O-phenylenediamine

ABSTRACT

Azo pigments of the Beta -hydroxynaphthoic acid series containing an o-phenylenediamine and a trimellitic acid imide moiety. These pigments are best illustrated by the formula   The pigments are suitable for example for coloring resins, surface coatings and printing inks and give brilliant hues of very good fastness properties.

United States Patent [1 1 Dimroth et al.

[ Dec. 16, 1975 [54] AZO PIGMENTS WITH AN ANTHRAQUINONYL COMPONENT AND A B-HYDROXYNAPHTHOIC ACID COMPONENT SUBSTITUTED BY A TRIMELLITIC ACID IMIDE VIA AN O-PHENYLENEDIAMINE [75] Inventors: Peter Dimroth, Ludwigshafen;

Manfred Gaeng, Bobenheim-Roxheim; Guenther Ruider, Ludwigshafen, all of Germany [73] Assignee: Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany [22] Filed: Oct. 19, I973 21 Appl. No.1 408,057

[30] Foreign Application Priority Data Sept. 21, 1973 Germany 2251747 [52] US. Cl 260/152; 260/40 R; 260/192;

260/202; 260/326 A; 260/326 N; 260/326 S; 106/22; 106/23', 106/288 Q [51] Int. Cl. C09B 29/36; C09B 43/12 [58] Field of Search 260/ 152 [56] References Cited UNITED STATES PATENTS 3,468,872 9/1969 Schefczik 260/152 FOREIGN PATENTS OR APPLICATIONS 1,224,739 3/1971 United Kingdom 260/152 Primary Examiner-Charles F. Warren Attorney, Agent, or Firm-Johnston, Keil, Thompson & Shurtleff [57] ABSTRACT Azo pigments of the B-hydroxynaphthoic acid series containing an o-phenylenediamine and a trimellitic acid imide moiety. These pigments are best illustrated by the formula The pigments are suitable for example for coloring resins, surface coatings and printing inks and give brilliant hues of very good fastness properties.

2 Claims, N0 Drawings A20 PIGMENTS WITH AN ANTHRAQUINONYL COMPONENT AND A HYDROXYNAPHTHOIC ACID COMPONENT SUBSTITUTED BY A TRIMELLITIC ACID IMIDE VIA AN O-PHENYLENEDIAMINE The invention relates to dyes of the formula (I):

tert.-butyl, benzyl, phenyl, phenyl substituted by fluoro, chloro, bromo, methyl, ethyl, isopropyl, methoxy, ethoxy, phenoxy, trifluoromethyl, phenyl, benzoyl, cyano, carbomethoxy, carbethoxy, carbamoyl, sulfonamido, acetylamino, benzoylamino, chlorobenzoylamino, methylbenzoylamino, acetoxy, benzoyloxy, methylsulfonyloxy, methylsulfonyl, methylmercapto or nitro, and naphthyl, and for example radicals of the formulae:

Particular industrial importance attaches to dyes of the formula (la):

OH -B HOG 0-H where A is the radical of l-aminoanthraquinone; R is hydrogen, chloro,methyl or methoxy; R is hydrogen or chloro; and B is hydrogen, methyl, ethyl, tert-butyl, phenyl or phenyl substituted by chloro, bromo, methyl, ethyl, isopropyl, methoxy, .ethoxy, cyano, carbomethoxy, carbethoxy, carbamoyl or sulfonamido.

The new pigments of the formula (I) are distinguished by excellent brilliance also in the full shade range and in addition they usually have excellent fastness to light and weathering and highly satisfactory fastness to overcoating and plasticizers.

Some of them have a hiding power unusual for an organic pigment so that they may also be used for purposes which hitherto were reserved for inorganic pigments, for example cadmium or lead compounds, because of the high hiding power of the latter.

The new dyes may be prepared:

a. by condensing an acyl halide of the formula (II):

@Qt (m COX where X Cl or Br with an amine or the formula (III):

B III C, m H N O or b. coupling the diazo compound of an amine of formula (IV):

A-N H, (IV) with a coupling component of formula (V):

The azo dye carboxylic acids on which the azo dye acid halides (II) are based may be prepared by a conventional method by coupling a diazonium salt of the amine (IV) with B-hydroxynaphthoic acid.

The azo dye carboxylic acids obtained in this way may be converted into the corresponding acid halides (ll) (chlorides or bromides) by treatment with phos phorus halides such as phosphorus pentachloride or phosphorus pentabromide, phosphorus trichloride, phosphorus oxychloride or preferably thionyl chloride.

The reaction may conveniently be carried out in an indifferent solvent such as nitrobenzene, a chlorinated benzene, toluene, a xylene, dimethylformamide or N- methylpyrrolidone; the addition of a catalytic amount of dimethylformamide or pyridine may be advantageous. I

The condensation of the azo carboxylic acid halide (II) with the amine (III) is advantageously carried out in an anhydrous medium, for example by heating the components in an organic solvent such as nitrobenzene, o-dichlorobenzene, trichlorobenzene, methyl benzoate, xylene, dimethylformamide, N-methylpyrrolidone and the like, and it is expedient to add an acid-binding agent such as sodium acetate or pyridine, or a catalytic amount of a compound which accelerates acylation, e.g. collidine, dimethylformamide and the like.

An expedient embodiment of the condensation is for example to dissolve the amine (III) prior to its addition in just sufficient solvent, preferably N-methylpyrrolidone or dimethylformamide, and then to add it to the azo acyl halide (II). The reverse sequence is also possible.

In a second embodiment, the dye (I) is obtained using a conventional method to couple, with a coupling component of the formula (V), a diazotized laminoanthroaquinone optionally substituted by chlorine in the 3-position or 4-position, or 2,4,5-trichloroaniline.

The coupling components of the formula (V) are obtained for example by condensation of 2-hydroxynaphthalene-3-carboxylic acid with an amine of the formula (III) in the presence of a chlorinating agent, for example phosphorus trichloride and thionyl chloride.

Coupling is conveniently effected by bringing together an aqueous alkaline solution of the coupling component (V) (or a very fine'ly divided suspension of the coupling component (V) in water), with or without the addition of an organic solvent, and an acid solution of the diazotized amine (IV). A pH range of from 4 to 7, advantageously set up by adding a buffer, for example sodium acetate, and the addition of wetting or dispersing agents, for example aralkyl sulfonates, facilitate a uniform reaction.

Pigment dyes according to the invention are obtained in this way in a very pure chemical condition but occasionally not in the physical form optimum for all purposes for which it may be used. They may be brought into a form suitable for the purpose in hand by conventional methods such as comminution, salt milling or recrystallization.

The new pigments may be used for the mass-coloration of, for example, viscose, for the production of colored print pastes for letterpress and offset printing, for the production of colored surface coatings, for example nitrocellulose, acrylate, melamine resin or alkyd resin coating compositions, for coloring phenol or amine plastics, thermoplastics such as polystyrene, polyolefins and PVC, and rubber or silicone resins, for coloring laminate paper or boards and for textile printmg.

The following Examples illustrate the invention and parts, unless otherwise stated, are parts by weight and the percentages are by weight; temperatures are given in Centigrade.

EXAMPLE 1 While stirring, 211 parts of the dye obtained by coupling diazotized l-aminoanthraquinone with 2-hydroxynaphthoic acid-3 is heated in 950 parts of nitrobenzene with 89 parts of thionyl chloride and 3 parts of dimethylformamide for 2 hours at C, and then for 3 hours at C. After the reaction mixture has cooled the uniform crystalline azo dye monocarboxylic acid chloride is isolated by suction filtration, washed with 300 parts of nitrobenzene, then with 200 parts of benzene and finally with 400 parts of cyclohexane, and dried at 80C at subatmosphen'c pressure. 195 parts of a red crystalline powder is obtained. Analysis: calculated 8.05% Cl; found 8.1% Cl.

220 parts of the azo dye monocarboxylic acid chloride prepared as described above is heated in 600 parts of nitrobenzene at 70C. 24.8 parts of finely powdered amine of the formula:

which has previously been dissolved in 100 parts of N-methylpyrrolidone is then added with gentle heating. The mixture is heated for 5 hours at C while stirring. After cooling to 80C the deposited sparingly soluble pigment is suction filtered, washed with nitrobenzene and then with methanol until the filtrate runs away clear. To obtain a water-moist paste the pigment is additionally washed with water. To improve the pigment it may (in the form of the methanol-moist product) be boiled for two hours in methanol or another solvent or stirred at ambient temperature.

After drying at 80C at subatmospheric pressure 37 parts of a red powder is obtained which is practically insoluble in the usual solvents. The pigment has the formula:

It colors PVC film and sheeting and surface coatings brilliant red hues having excellent fastness to light, migration and overcoating. The excellent brilliance which can be achieved in the case of strong dyeings (full shade) is particularly noteworthy.

35926343 5 6 Other monoazo pigments are obtained with the cominto the. acid halide and condensing this with 1 mole of ponents given in the following Table by coupling 1 th amine ifi d i column II, mole of the diazo compound of the amine specifiedin I V I column I with 1 mole of 2-hydroxynaphthoic acid-3, Column Ill gives the hue of a surface coating preconverting the monoazo dye carboxylic acid obtained 5 pared with the pigment obtained.

I II III 0 2 w NHOC I o H N red 2 H N O NHO ll reddish brown 0 CH H N 5 l NHOC 6 CH L n H2N\ maroon o -CH 5 red 5 NHOC I H N p -Q NH0 71 5 O 6 '1 H2 bluish red CH3 NHOC Q reddish brown 7 H 7 CH :0i1-tinued"" 1 u Y I EX. I III NHOC 5 8 H2115 red 9 11 HEN C1 red N- NHOC red 0 c1 H2N\H/\K\ c51 @q- ;1 red NHOC 11 HEN 0 (:1

0 01 K)? Q 12 2 0 C1 bluish red NHOC 01 13 -continued III NHOC

bluish red OCH3 red

O' CH red bluish red m 0 1) H C 2/ H C O C O 2) W C 2 C O H H Hz) N AH Hv C N 2 H 5 w: 2

red

-continued III red

bluish red NHOC H N@ 1 red NHOC- red maroon NHOC o -continued EX. I II III 0 I NH0 8 OCH bluish red H N 2 H N Cl NH0 0 H N 2 red gig" Q 3 bluish red I NHOC O OCH 3 NHOC bluish red OCH -OCH NHOC/ 3 :F Q 3 O 2 5 bluish red OCH @5 NHOC O 2 red 0 CH NHO S bluish red E :l OCH Ex. I

-continued II III O 6 @Q 5; 5 gig; m 0 0 H N O bluish red CH v -CH 3 f NHOC H N brownish red.

CH NHOC v CH 2 ii red 0 CH5 H2N red -CH m Q 3 maroon NHOC O H N I C0ntinued EX. I II III m- G 72 NHOC O H N H2N o 2 (5 red 0 c1 NHOC g c1 73 H2N\ bluish red II 7 NHOC O bluish red 00H H2N NI-IOC g d OCH} re H2N\ OCH Q 5 red NHOC O 76 II I l 3 NHOC o ocH H bluish 77 H red 00H m" bluish red NHOC 5 -Continued EX. I II III A l I CH5 NHOC l 79 H 0 red H N O 2 Q B 8O NHO red ii bluish 81 NHOC O OCH red 0 Cl 6 NHOC 6 82 red Cl I 9 NHOC J: bluish red O 85 n H N ocH 8 n NHOC O OCH bluish red 0 Cl 2@' @OCH} 85 NHOC E I OCH bluish red Continued EX. I II III CF 0 G W a I H red H N o 2 7 n NHOC O 8 red NH0 88 H 2 red 0 ll NHOC H W O 89 n brownish red CH O NHOC' O C 90 H N 3 red 91 red NHOC 2 0 c1 OCH3 Continued EX. II III 0 c1 93 Q QNQ bluish red NHOC OCH3 I! 94 NHOCQi; l brown OCH3 0 Cl 95 @NQ Cl brownish red NHOC 2 0 c1 l OCH 0 Cl 96 /@Nj bluish red NHOC H N 2 O CH3 O l 97 bluish red HOC H2N OCH 98 N red H N NHOC O OCH5 0 99 Qi) ocH bluish red OCH Continued EX. II III 100 N bluish red NHOC H N OCH OCH

101 bluish red Q NHOC OCH OCH 102 bluish red NHOC O OCH OCH 103 N-CH red NHOC 3 F 5 10 a red E NHOC CH OCH 0 CH3 1.05 1601a red NHOC H N OCH 

1. AN AZO PIGMENT OF THE FORMULA
 2. The azo pigment having the formula 